Heat-resistant metal component, method for manufacturing the same, and high-temperature apparatus

Abstract

To provide a heat resistant metal member capable of: using various kinds of metal bases; continuously obtaining a diffusion barrier function in a high temperature oxidizing atmosphere or high temperature corrosive atmosphere; continuously maintaining a protective oxide film on the outermost surface over a long period, thereby; and replacing even a process required for manufacturing with a simple process, such as electroplating method, and a method for manufacturing the same.SOLUTION: A heat resistant metal member includes: a boundary layer (200) including Co on a metal base (100); a diffusion barrier layer (300) including a Re containing Co-based alloy as a main component; and an Al containing alloy layer (500) in this order. A method for manufacturing the heat resistant metal member comprises: forming a Co film, a Re (Ni) film and a Co film or a Ni film in this order on the metal base by an electroplating method; burying and heating the metal base into a powder mixture including Cr powder and Al2O3 powder to form the diffusion barrier layer; and subjecting the diffusion barrier layer to Al diffusion to form an Al containing alloy layer on the diffusion barrier layer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to heat-resistant metal components, methods for manufacturing the same, high-temperature equipment, and plating solutions, and is particularly suitable for use in incinerators, exhaust gas system components, boilers, internal combustion engines, gas turbines, jet engines, satellite thruster engines, fuel cells, etc., which are used in high-temperature oxidizing or high-temperature corrosive atmospheres. [Background technology]

[0002] Heat-resistant alloy substrates used in various combustion equipment, internal combustion engines, boilers, incinerators, exhaust gas system components, turbines, jet engines, fuel cells, etc., are coated with high-temperature oxidation-resistant coatings. Typical coatings include Al-containing alloy coatings that form protective alumina (Al2O3) [(Ni-Al alloy coating (β-NiAl), γ'-(Ni,Pt)3Al (or Pt-added γ'-Ni3Al), MCrAlY (M=Ni,Co), etc.)] and Cr-containing alloy coatings that form protective chromia (Cr2O3) [γ-Ni(Cr), Fe-Cr, etc.].

[0003] However, the Al-containing alloy coating described above loses its high-temperature oxidation resistance prematurely when used at high temperatures due to a decrease in Al concentration (see Non-Patent Document 1).

[0004] To suppress the decrease in Al concentration in the Al-containing alloy film, the present inventors have proposed a technique in which a Re-Cr-Ni-based σ-phase diffusion barrier layer (referred to as a σ-Re barrier) is formed on a substrate, and then an Al-containing Ni-based alloy layer is laminated on its surface. The σ-Re barrier and the Al-containing Ni-based alloy layer together are referred to as Diffusion Barrier Coating (DBC), and the substrate, diffusion barrier, Al-containing Ni-based alloy layer, and protective alumina film are collectively referred to as a Diffusion Barrier Coating System. Details of the diffusion barrier layer are described in Patent Documents 1 to 4.

[0005] In the σ-Re barriers described in Patent Documents 1 to 4, the Re-Cr-Ni σ-phase is composed of a continuous single layer. When exposed to high temperatures for extended periods, voids form in the boundary layer between the Ni-based single-crystal superalloy and the σ-Re barrier, and cracks may simultaneously occur within the diffusion barrier layer. Therefore, Patent Documents 5 to 7 propose a three-layer structure in which the diffusion barrier layer has a double-phase structure of Re-Cr-Ni σ-phase and Ni-Cr γ-phase, with the σ-phase precipitated within the matrix phase of the γ-phase, forming a discontinuous form of the so-called σ-Re layer.

[0006] The phenomenon of void formation and growth in the boundary layer between the substrate and the σ-Re barrier layer during the above-mentioned high-temperature, long-duration heating process is also observed in σ-Re barrier coatings formed on Ni-based heat-resistant alloys (for example, Ni-25Cr-20Fe-10Mo alloy (mass%)). Regarding this problem, Patent Document 8 proposes that void formation can be suppressed by increasing the thickness of the Ni layer inserted between the substrate and the σ-Re barrier layer to 60 μm or more.

[0007] The γ-Ni(Cr) phase constituting the diffusion barrier layer described in Patent Documents 5-7 serves as a diffusion pathway between the Al in the Al-containing alloy layer and elements contained in the substrate, and therefore exhibits inferior diffusion barrier performance compared to the σ-Re system barrier described in Patent Documents 1-4. Increasing the thickness of the Ni layer described in Patent Document 8 causes the Cr and Re of the σ-Re system barrier to solid dissolve in the Ni layer, accelerating the decomposition and disappearance of the σ-Re system barrier and resulting in a loss of diffusion barrier performance.

[0008] Patent documents 1 to 8 employ high and low heat treatment temperatures, respectively, to form the diffusion barrier layer. Specifically, the σ-Re barriers in patent documents 1 to 4 and 8 are formed at relatively high temperatures (above 1200°C), which can cause structural changes in the substrate and grain coarsening. On the other hand, the diffusion barrier layers in patent documents 5 to 7, in which the σ-phase is precipitated within the γ-phase, can be formed by heat treatment at relatively low temperatures (below 1120°C), thus suppressing structural changes and grain coarsening. However, even with a three-layer structure, their diffusion barrier performance is inferior.

[0009] On the other hand, the following problems have been pointed out regarding Cr-containing alloy coatings [(Fe-Cr, γ-Ni(Cr)]. Specifically, stainless steel (Fe-Cr, Fe-Cr-Ni) is used as the Cr-containing alloy, and it forms a protective film of Cr2O3. However, according to Non-Patent Literature 2, it is known that in harsh corrosive environments such as oxidation (O2, H2O, etc.) and carburizing (CH4, etc.) at high temperatures (above 1000°C), it prematurely loses its properties. Therefore, as a coating, a Cr-containing Ni-based alloy coating is formed by a Cr pack treatment method in which a mixed powder of (Cr+NH4Cl+Al2O3) is heat-treated. However, depending on the shape of the component, for example, a high Cr (α-Cr phase) layer is formed at corners, which is problematic as it induces cracks and delamination. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Patent No. 3857689 [Patent Document 2] Patent No. 3857690 [Patent Document 3] Patent No. 3910588 [Patent Document 4] Patent No. 4753720 [Patent Document 5] Patent No. 5905336 specification [Patent Document 6] Patent No. 5905354 specification [Patent Document 7] Patent No. 5905355 specification [Non-patent literature]

[0011] [Non-Patent Document 1] "Heat-resistant coatings for jet engines," Issei Otera, Yoshihiro Tsuda, Takato Araki, Nobuyoshi Mori, and Akihiro Sato; Surface Technology, Vol. 63, No. 1, pp. 19-23, (2012) [Non-Patent Document 2] Supervised by Shoji Nakamori, High-Temperature Corrosion Cases Caused by Boiler Combustion Gas and Countermeasures Therefor, ISBN978-4-924728-66-OC 3050

Summary of the Invention

Problems to be Solved by the Invention

[0012] As described above, since heat treatment at a high temperature of 1200°C or higher is required for the formation of the σ-Re-based barrier in Patent Documents 1 to 4 and 8, there is a possibility of causing changes in the structure of the base material and coarsening of crystal grains. Therefore, the base material is limited to single crystals such as Ni-based single crystal superalloys, and it has been difficult to use general-purpose base materials typified by Fe-based alloys such as stainless steel and Ni-based alloys such as Hastelloy. Further, in Patent Documents 5 to 7, although the temperature of the heat treatment required for the formation of the diffusion barrier layer was low, the diffusion barrier ability was low. Furthermore, regarding the Cr-containing alloy film, it is inevitable to form a high-Cr α-Cr phase that induces cracks and peeling in the Cr-containing Ni-based alloy film formed by the Cr pack treatment method.

[0013] Therefore, the problem to be solved by this invention is that various metal base materials including general-purpose base materials can be used, and when used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, the diffusion barrier function can be continuously obtained, so that a protective oxide film can be continuously maintained on the outermost surface for a long time. Furthermore, especially when a Cr-containing alloy layer is used, cracks and peeling of the protective oxide film can be suppressed, and the manufacturing process required is also a simple process such as a plating method or a pack treatment method. It is to provide a heat-resistant metal member and its manufacturing method, a high-temperature device including such a heat-resistant metal member, and a plating solution suitable for use in the manufacturing method of the heat-resistant metal member.

Means for Solving the Problems

[0014] To solve the above problems, this invention provides a metal base material, and a diffusion barrier layer mainly composed of a Co-based alloy containing Re on the above metal base material, and At least a boundary layer containing Co between the above-mentioned metal substrate and the above-mentioned diffusion barrier layer, An Al-containing alloy layer or a Cr-containing alloy layer on the above-mentioned diffusion barrier layer, which is a heat-resistant metal member having the above.

[0015] The Re concentration in the diffusion barrier layer is typically 1 atomic % or more. The diffusion barrier layer preferably consists of a continuous α-Co(Re) layer containing 10 atomic % of Re, and the α-Co(Re) continuous layer contains precipitates of the ε-Re(Co) phase. Here, Co(Re) means Co containing Re and is synonymous with a Co-Re alloy. The same applies to Re(Co) and Re(Ni) described later. The thickness of the diffusion barrier layer is selected as required, but is typically 10 μm or more and 100 μm or less. The diffusion barrier layer may contain one or more elements contained in the metal substrate and the Al-containing alloy layer or the Cr-containing alloy layer in addition to Re and Co. In this case, when the ε-Re(Co) phase contains Ni in addition to Co, for example, it is described as the ε-Re(Co,Ni) phase, but the ε-Re(Co) phase shall include the ε-Re(Co,Ni) phase. The same applies when the ε-Re(Co) phase contains other elements in addition to Co and Ni.

[0016] When an Al-containing alloy layer is present on the diffusion barrier layer, this Al-containing alloy layer may also contain Pt. In this case, the Pt concentration in the Al-containing alloy layer is typically 1.5 atomic percent or more. By including Pt in the Al-containing alloy layer in this way, the Al concentration in the Al-containing alloy layer can be maintained at a high level during use of the heat-resistant metal component. By including Co in the boundary layer, the formation of voids in the boundary layer during use of the heat-resistant metal component can be suppressed. In this case, the boundary layer typically contains Al. The Al concentration in this boundary layer is typically 1 atomic percent or more, but preferably 3 atomic percent or more and 25 atomic percent or less. When the boundary layer contains Al in this way, the decomposition of the Al-containing alloy layer is delayed during use of the heat-resistant metal component, thus preventing a decrease in the Al concentration. Furthermore, because the solubility of Re in the Al-containing alloy layer is low, the Al contained in the boundary layer suppresses the decomposition of the diffusion barrier layer, thus stably maintaining the diffusion barrier layer. There are no particular restrictions on the thickness of the boundary layer, but it is typically 5 μm to 200 μm, preferably 10 μm to 100 μm.

[0017] The Al-containing alloy layer forms a protective alumina (Al2O3) on the outermost surface of the heat-resistant metal component when it is used, protecting the entire heat-resistant metal component, including the metal substrate, boundary layer, and diffusion barrier layer, from high-temperature oxidizing and high-temperature corrosive atmospheres. The Al-containing alloy layer is not particularly limited, but for example, it can consist of β-NiAl, γ'-Ni3Al, CoAl, FeAl, etc., and typically, the elements other than Al are mainly Co and Ni. The Al-containing alloy layer may inevitably contain elements contained in the metal substrate, boundary layer, and diffusion barrier layer. The Al concentration in the Al-containing alloy layer is not particularly limited, but is typically between 10 atomic% and 60 atomic%. The thickness of the Al-containing alloy layer is selected as needed, but is typically between 20 μm and 100 μm. The Cr-containing alloy layer forms a protective chromia (Cr2O3) on the outermost surface of the heat-resistant metal component when it is used, protecting the entire heat-resistant metal component, including the metal substrate, boundary layer, and diffusion barrier layer, from high-temperature oxidizing and high-temperature corrosive atmospheres. The Cr-containing alloy layer typically consists of NiCrAl, FeCrAl, or Ni-Al alloys containing Cr particles, and typically has Co and Ni as the main elements other than Cr. The Cr-containing alloy layer may also inevitably contain elements contained in the metal substrate, boundary layer, and diffusion barrier layer. The Cr concentration in the Cr-containing alloy layer is not particularly limited, but is typically between 10 atomic% and 50 atomic%. The thickness of the Cr-containing alloy layer is selected as needed, but is generally between 20 μm and 100 μm.

[0018] This heat-resistant metal component may further have a transition layer between the diffusion barrier layer and the Al-containing alloy layer or the Cr-containing alloy layer. This transition layer typically has an Re concentration of less than 1 atomic percent and an Al or Cr concentration of 10 atomic percent or less, but is not limited to this.

[0019] The metal substrate can be selected as needed and various types can be used, but examples include Fe-based alloys, Co-based alloys, Ni-based alloys, Ni-based single-crystal superalloys, etc. Of these, Fe-based alloys include, for example, SUS304, SUS310, etc., Co-based alloys include, for example, alloys mainly composed of Co and containing Cr, W, etc., and alloys mainly composed of Co and containing Mo, Cr, Si, Fe, etc., etc., and Ni-based alloys include, for example, Hastelloy-X, Inconel, etc. The shape of the metal substrate is not particularly limited and is selected according to the application, etc., but examples include flat plates, rods (square bars, round bars, etc.), tubular shapes, box shapes, etc.

[0020] Heat-resistant metal components are not particularly limited, but specific examples include components for incinerators, boilers, gas turbines, jet engines, exhaust gas system components, and so on.

[0021] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, A step of forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer, which is at least mainly composed of a Co-based alloy containing Re, by embedding the metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or the Ni film are formed in a mixed powder containing Cr powder and Al2O3 powder and performing heat treatment. A step of forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer and the diffusion barrier layer are formed, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0022] The plating method refers to the electroplating method. The temperature and time for the heat treatment of the metal substrate on which the first Co film, Re(Ni) film and the second Co film or Ni film have been formed are selected as needed, but the temperature is, for example, 1050°C to 1150°C, and the time is, for example, 1 hour to 20 hours, typically 2 hours to 12 hours. This heat treatment is preferably carried out in an inert gas atmosphere. The inert gas atmosphere is not particularly limited, but is preferably a mixed gas of Ar (argon) and He (helium) or a mixed gas of Ar and H2 (hydrogen), and in particular a mixed gas of Ar and 3 vol% H2 is preferred. The temperature and time for the Al diffusion treatment are selected as needed, but the temperature is, for example, 950°C to 1100°C, typically 1000°C to 1050°C, and the time is, for example, 1 hour to 20 hours. This Al diffusion treatment is also preferably carried out in an inert gas atmosphere similar to that described above.

[0023] In this invention, matters other than those described above are considered to have been explained in relation to the invention of the heat-resistant metal member, as long as they do not contradict its properties.

[0024] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least a Co-based alloy containing Re as its main component, and an Al-containing alloy layer on the diffusion barrier layer, by embedding the metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or the Ni film are formed in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and heat-treating it, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0025] In this invention, a metal substrate is embedded in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and subjected to heat treatment. This process allows for Al diffusion, forming an Al-containing alloy layer, by generating Al and TiO through the reaction of Ti with Al2O3, or by generating Al and MgO through the reaction of Mg with Al2O3. If necessary, powders of Al sources such as FeAl and NiAl may be mixed into the mixed powder.

[0026] The temperature, time, and atmosphere for the heat treatment of the metal substrate on which the first Co film, Re(Ni) film, and the second Co film or Ni film are formed are the same as those in the invention for the method of manufacturing a heat-resistant metal member described above.

[0027] When incorporating Pt into an Al-containing alloy layer, for example, a Pt film is formed on a second Co film by a plating method, or Pt powder (e.g., particle size of about 1 μm) is applied by a slurry method. By doing so, an Al-containing alloy layer containing Pt can be formed by heat treatment.

[0028] In this invention, matters other than those described above are considered to have been described in relation to the invention of the heat-resistant metal member and the invention of the method for manufacturing the heat-resistant metal member, as long as they do not contradict the properties.

[0029] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least a Co-based alloy containing Re as its main component, and an Al-containing alloy layer on the diffusion barrier layer, by embedding the metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed in a mixed powder containing Ni powder, NiAl powder, NH4Cl powder, and Al2O3 powder and heat-treating it, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0030] The temperature, time, and atmosphere for the heat treatment of the metal substrate on which the first Co film, Re(Ni) film, and the second Co film or Ni film are formed are the same as those in the invention for the method of manufacturing a heat-resistant metal member described above.

[0031] In this invention, as long as it does not contradict its properties, the above-described inventions relating to the heat-resistant metal member and the method for manufacturing the heat-resistant metal member are considered valid.

[0032] Furthermore, this invention, A step of forming a Co-Re alloy film containing at least Ni on a metal substrate by a plating method using a plating solution which is a mixture of a Co plating solution and a Re(Ni) plating solution, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least a Co-based alloy containing Re as its main component, and an Al-containing alloy layer on the diffusion barrier layer by embedding the metal substrate on which the above-mentioned Co(Re) alloy film is formed in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and performing heat treatment, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0033] The mixing ratio (vol%) of Co plating solution (electrolyte containing Co ions) and Re(Ni) plating solution (electrolyte containing Re and Ni ions) in the plating solution is selected as needed, but is typically in the range of 10 vol% Co plating solution, 90 vol% Re(Ni) plating solution to 60 vol% Co plating solution, 40 vol% Re(Ni) plating solution, and preferably in the range of 20 vol% Co plating solution, 80 vol% Re(Ni) plating solution to 50 vol% Co plating solution, 50 vol% Re(Ni) plating solution. By performing plating using such a plating solution, Co-Re alloy films containing Ni of various compositions can be formed.

[0034] The heat treatment performed by immersion in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder is as described above in relation to the invention.

[0035] In this invention, matters other than those described above are considered to have been described in relation to the invention of the heat-resistant metal member and the invention of the method for manufacturing the heat-resistant metal member, as long as they do not contradict the properties.

[0036] Furthermore, this invention, A step of forming at least a Co(Re) alloy film containing Ni on a metal substrate by a plating method using a plating solution which is a mixture of a Co plating solution and a Re(Ni) plating solution, The process involves forming a Co film on the above Co-Re alloy film by a plating method, A step of simultaneously forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer, which is at least mainly composed of a Co-based alloy containing Re, by embedding the above-mentioned Co-Re alloy film and the above-mentioned metal substrate on which the Co film is formed in a mixed powder containing Cr powder and Al2O3 powder and performing heat treatment, A step of forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer and the diffusion barrier layer are formed, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0037] The temperature, time, and atmosphere of the heat treatment are as described above in relation to the invention.

[0038] In this invention, matters other than those described above are considered to have been described in relation to the invention of the heat-resistant metal member and the invention of the method for manufacturing the heat-resistant metal member, as long as they do not contradict the properties.

[0039] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, a second Co film, and a Ni film on a metal substrate by a plating method, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least a Co-based alloy containing Re as its main component, and a Cr-containing alloy layer on the diffusion barrier layer, by embedding the metal substrate on which the first Co film, the Re(Ni) film, the second Co film, and the Ni film are formed in a mixed powder containing Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder and heat-treating it, A step of forming an Al-containing alloy layer on the Cr-containing alloy layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer, the diffusion barrier layer, and the Cr-containing alloy layer are formed, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0040] In this invention, as long as it does not contradict its properties, the above-described inventions relating to the heat-resistant metal member and the method for manufacturing the heat-resistant metal member are considered valid.

[0041] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least a Co-based alloy containing Re as its main component, and a Cr-containing alloy layer on the diffusion barrier layer, by embedding the metal substrate on which the first Co film, the Re(Ni) film, and the second Co film are formed in a mixed powder containing Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder and heat-treating it, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0042] In this invention, as long as it does not contradict its properties, the above-described inventions relating to the heat-resistant metal member and the method for manufacturing the heat-resistant metal member are considered valid.

[0043] Furthermore, this invention, A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer having at least Re-containing Co-based alloy as its main component, and a Cr-containing alloy layer on the diffusion barrier layer, by applying a slurry containing at least Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder to the second Co film described above, and then immersing the metal substrate coated with the slurry in the mixture containing Cr powder and Al2O3 powder and performing heat treatment, This is a method for manufacturing a heat-resistant metal component having [a specific characteristic].

[0044] In this invention, as long as it does not contradict its properties, the above-described inventions relating to the heat-resistant metal member and the method for manufacturing the heat-resistant metal member are considered valid.

[0045] Furthermore, this invention, Metal substrate and A diffusion barrier layer on the above metal substrate, comprising at least a Co-based alloy containing Re as the main component, A boundary layer containing at least Co between the above metal substrate and the above diffusion barrier layer, The above diffusion barrier layer includes an Al-containing alloy layer or a Cr-containing alloy layer, Heat-resistant metal member having It is a high-temperature device having [a certain characteristic].

[0046] High-temperature devices may include various types that partially or entirely incorporate the heat-resistant metal components mentioned above, but specifically, examples include gas turbines, jet engines, exhaust gas systems, boilers, heat treatment furnaces, incinerators, etc.

[0047] In this invention of the high-temperature apparatus, unless otherwise stated, the explanations described above in relation to the invention of the heat-resistant metal member are valid.

[0048] Furthermore, this invention, This is a plating solution obtained by mixing Co plating solution and Re(Ni) plating solution.

[0049] In this invention, the explanation is valid in relation to the invention of a method for manufacturing the above-mentioned heat-resistant metal member using this plating solution. [Effects of the Invention]

[0050] According to this invention, a heat-resistant metal component can continuously obtain a diffusion barrier function by having a boundary layer containing at least Co, a diffusion barrier layer mainly composed of a Co-based alloy containing Re, and an Al-containing alloy layer or a Cr-containing alloy layer on a metal substrate. Therefore, when used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, a protective oxide film can be maintained on the outermost surface for a long period of time. In particular, when a Cr-containing alloy layer is used, cracking and peeling of the protective oxide film can be suppressed. Furthermore, since the heat-resistant metal component can be manufactured at a temperature of 1100°C or less, including the formation of the diffusion barrier layer, various metal substrates, including general-purpose substrates made of Fe-based alloys, Co-based alloys, Ni-based alloys, etc., can be used. The manufacturing process can also be kept low as it only requires simple processes such as plating and packing. [Brief explanation of the drawing]

[0051] [Figure 1] This is a cross-sectional view showing a heat-resistant metal member according to the first embodiment of this invention. [Figure 2] This is a cross-sectional view showing a heat-resistant metal member according to the first embodiment of this invention. [Figure 3] This is a cross-sectional view showing a first example of a method for manufacturing a heat-resistant metal member according to a first embodiment of the present invention. [Figure 4] This is a cross-sectional view showing a first example of a method for manufacturing a heat-resistant metal member according to a first embodiment of the present invention. [Figure 5] This is a cross-sectional view showing a fifth example of a method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. [Figure 6] This is a cross-sectional view showing a seventh example of a method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. [Figure 7]This is a cross-sectional view showing an eighth example of a method for manufacturing a heat-resistant metal member according to the first embodiment of the present invention. [Figure 8] This is a cross-sectional view showing a heat-resistant metal member according to a second embodiment of the present invention. [Figure 9] This is a cross-sectional view showing a heat-resistant metal member according to a second embodiment of the present invention. [Figure 10A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after plating and heat treatment in Example 1. [Figure 10B] Figure 10A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 11A] This is a photograph used as a substitute for a drawing, showing a magnified view of a portion of the metal substrate shown in Figure 10A. [Figure 11B] Figure 11A is a schematic diagram showing the measurement results of the concentration distribution of Re in the cross-section of the metal substrate. [Figure 12] This is a simplified diagram showing the Co-Re binary system phase diagram. [Figure 13A] Figure 10A is a photographic representation of the cross-sectional structure after Al diffusion treatment, which was performed after an additional Ni film was formed on the metal substrate shown in Figure 10A. [Figure 13B] Figure 13A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 14A] This is a photograph serving as a drawing to show the cross-sectional structure of the metal substrate in Example 2 after plating, heat treatment, additional Ni plating, and Al diffusion treatment. [Figure 14B] Figure 14A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 15A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after plating and heat treatment in Example 3. [Figure 15B] Figure 15A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 16A] Figure 15A is a photographic representation of the cross-sectional structure after Al diffusion treatment, which was performed after an additional Ni film was formed on the metal substrate shown in Figure 15A. [Figure 16B]Figure 16A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 17A] This is a photograph used as a substitute for a drawing, showing a magnified view of a portion of the metal substrate shown in Figure 16A. [Figure 17B] Figure 17A is a schematic diagram showing the measurement results of the concentration distribution of Re in the cross-section of the metal substrate. [Figure 18A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after plating and Ti treatment in Example 4. [Figure 18B] Figure 18A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 19A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after plating and Ti treatment in Example 5. [Figure 19B] Figure 18A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 20A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate in Example 6 after plating and (Ti+Mg) treatment. [Figure 20B] Figure 20A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 21A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate in Example 7 after plating and (Ti+FeAl) treatment. [Figure 21B] Figure 21A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 22A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 8 after plating and (Ti+NiAl) treatment. [Figure 22B] Figure 22A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 23A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate in Example 9 after plating and (Ti+NiAl) treatment. [Figure 23B] Figure 23A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 24A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 10 after plating and (Ti+NiAl) treatment. [Figure 24B] Figure 24A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 25A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate in Example 11 after plating and (Ti+NiAl) treatment. [Figure 25B] Figure 25A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 26A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 12 after plating and (Ti+NiAl) treatment. [Figure 26B] Figure 26A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 27A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 13 after plating and (Ti+NiAl) treatment. [Figure 27B] Figure 27A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 28] This is a schematic diagram showing the dependence of the Al, Ni, and Co concentrations in the Al-containing alloy layer on the Pt concentration added to the Al-containing alloy layer, as determined from the results of Examples 9 to 13. [Figure 29A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 14 after plating and (Ni+NiAl) treatment. [Figure 29B] Figure 29A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 30A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 15 after plating and (Cr+Ni) treatment. [Figure 30B] Figure 30A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 31A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after FeAl treatment in Example 15. [Figure 31B] Figure 31A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 32A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate in Example 16 after plating and (Cr+Ni) treatment. [Figure 32B] Figure 32A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 33A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after FeAl treatment in Example 16. [Figure 33B] Figure 33A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 34A] This is a photograph in lieu of a drawing showing the cross-sectional structure of a metal substrate after plating using plating solution (1) in Example 17. [Figure 34B] Figure 34A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 35A] This is a photograph in lieu of a drawing showing the cross-sectional structure of a metal substrate after plating using plating solution (1) in Example 17. [Figure 35B] Figure 35A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 36A] This is a photograph in lieu of a drawing showing the cross-sectional structure of a metal substrate after plating using the plating solution (2) in Example 17. [Figure 36B] Figure 36A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 37A] This is a photograph in lieu of a drawing showing the cross-sectional structure of a metal substrate after plating using the plating solution (2) in Example 17. [Figure 37B] Figure 37A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 38A] This is a photograph in lieu of a drawing showing the cross-sectional structure of a metal substrate after plating using the plating solution (3) in Example 17. [Figure 38B]Figure 38A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 39] This is a schematic diagram showing the relationship between the volume ratio of Co plating solution in the plating solution and the concentrations of Co, Re, and Ni in the plating film, as determined from the results of Example 17. [Figure 40A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate after Ti treatment, as shown in Figure 34A of Example 18. [Figure 40B] Figure 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 41A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate after Ti treatment, as shown in Figure 35A of Example 19. [Figure 41B] Figure 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 42A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate after Ti treatment, as shown in Figure 37A of Example 20. [Figure 42B] Figure 40A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 43A] This is a photograph serving as a substitute for a drawing, showing the cross-sectional structure of the metal substrate after plating and heat treatment in Example 21. [Figure 43B] Figure 43A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 44A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate in Example 22 after plating and heat treatment. [Figure 44B] Figure 44A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Figure 45A] This is a photograph in lieu of a drawing showing the cross-sectional structure of the metal substrate after plating and heat treatment in Example 23. [Figure 45B] Figure 45A is a schematic diagram showing the measurement results of the concentration distribution of each element in the cross-section of the metal substrate. [Modes for carrying out the invention]

[0052] The following describes embodiments for carrying out the invention (hereinafter simply referred to as "embodiments").

[0053] <First Embodiment> [Heat-resistant metal components] Figure 1 shows a heat-resistant metal member according to the first embodiment. As shown in Figure 1, in this heat-resistant metal member, a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500 are laminated in this order on the surface of a metal substrate 100. A transition layer 400 may also exist between the diffusion barrier layer 300 and the Al-containing alloy layer 500, and the laminated structure in that case is shown in Figure 2.

[0054] The metal substrate 100 is selected as needed, for example from those already listed, but specifically, it consists of, for example, Fe-based alloys, Co-based alloys, Ni-based alloys, Ni-based single-crystal superalloys, etc. The boundary layer 200 contains at least Co, and is a layer that also contains one or more elements that constitute the metal substrate 100, one or more elements that constitute the diffusion barrier layer 300, and possibly one or more elements that constitute the Al-containing alloy layer 500. The boundary layer 200 may or may not contain Al. When the boundary layer 200 contains Al, if the Al concentration of the boundary layer 200 exceeds 25 atomic%, voids are more likely to form between the boundary layer 200 and the diffusion barrier layer 300 when the heat-resistant metal member is used, so the Al concentration is typically selected to be 25 atomic% or less, preferably 15 atomic% or less. The presence of Al in the boundary layer 200 can suppress the decomposition of the diffusion barrier layer 300 by the diffusion of Re and the decomposition of the Al-containing alloy layer 500 by the diffusion of Al. The diffusion barrier layer 300 is made of a Co-based alloy containing Re, and contains one or more elements that constitute the metal substrate 100 and one or more elements that constitute the Al-containing alloy layer 500. Typically, it has a structure in which an ε-Re(Co) phase is precipitated in a continuous layer of α-Co(Re) phases containing 10 atomic percent of Re. The diffusion barrier layer 300 helps maintain the Al concentration of the Al-containing alloy layer 500 when the heat-resistant metal component is used, and also helps to form and maintain protective Al2O3, and has excellent regeneration ability. The Al-containing alloy layer 500 is typically mainly composed of Co and Ni in addition to Al, and contains one or more elements that constitute the metal substrate 100 and one or more elements that constitute the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is not particularly limited, but is typically between 10 atomic percent and 60 atomic percent. The Al-containing alloy layer 500 may also contain, for example, 1.5 atomic percent or more of Pt. The Pt in the Al-containing alloy layer 500 has the function of maintaining a high Al concentration, thereby ensuring oxidation resistance. The transition layer 400 is a layer containing one or more elements that constitute the diffusion barrier layer 300 and one or more elements that constitute the Al-containing alloy layer 500.The thickness of the boundary layer 200 is not particularly limited, but is typically 5 μm to 200 μm, and more typically 10 μm to 100 μm. The thickness of the diffusion barrier layer 300 is selected as needed, but is preferably 10 μm to 100 μm. The thickness of the transition layer 400 is not particularly limited. The thickness of the Al-containing alloy layer 500 is selected as needed, but is typically 20 μm to 100 μm.

[0055] [Method for manufacturing heat-resistant metal components] This section describes the manufacturing method for this heat-resistant metal component. Here, we will explain the first to seventh examples of the manufacturing method (Manufacturing Methods 1 to 7).

[0056] (1) Manufacturing method 1 As shown in Figure 3, first, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on the metal substrate 100 by a plating method. The Ni strike film is formed for purposes such as improving the adhesion of the plating film to the metal substrate 100, and the plating is performed at, for example, a current density of 0.5 A / cm². 2 Perform the process for 1 minute. Plating of the first Co film 110 and the second Co film 130 is typically done at a current density of 0.03 A / cm². 2 Perform the process for 10-25 minutes. Plating of Re(Ni) film 120 is typically done at a current density of 0.04 A / cm². 2 This process is carried out for 10 to 60 minutes. Sometimes a Ni film is formed instead of the second Co film 130.

[0057] Next, the metal substrate 100 on which the first Co film 110, Re(Ni) film 120, and second Co film 130 are formed is embedded in a mixed powder containing Cr powder and Al2O3 powder (for example, (10-15) mass% Cr powder + (90-85) mass% Al2O3 powder) and subjected to heat treatment to form a boundary layer 200 and a diffusion barrier layer 300, as shown in Figure 4. The heat treatment temperature is, for example, 1050°C to 1150°C (for example, 1100°C), and the time is, for example, 2 hours to 12 hours. The heat treatment atmosphere is an inert gas atmosphere, preferably, for example, an Ar + 3 vol% H2 atmosphere.

[0058] Next, an Al diffusion treatment is performed on the metal substrate 100 on which the boundary layer 200 and diffusion barrier layer 300 have been formed, thereby forming an Al-containing alloy layer 500 on the diffusion barrier layer 300, as shown in Figure 1. The Al diffusion treatment is performed by immersing the metal substrate 100 on which the boundary layer 200 and diffusion barrier layer 300 have been formed in a mixed powder containing, for example, FeAl powder, NH4Cl powder, and Al2O3 powder (for example, (10-15) mass% FeAl powder + (1-2) mass% NH4Cl powder + (89-83) mass% Al2O3 powder), and heating it in an inert gas atmosphere, preferably an Ar+3vol%H2 atmosphere, at a temperature of 950°C to 1100°C, preferably 1000°C to 1050°C, for 1 to 10 hours. This Al diffusion treatment can form an Al-containing alloy layer 500 with an Al concentration of, for example, 50 atomic% to 60 atomic%. During the formation of this Al-containing alloy layer 500, a transition layer 400, which is a mixture of the two, may be formed between the diffusion barrier layer 300 and the Al-containing alloy layer 500.

[0059] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0060] (2) Manufacturing method 2 First, in the same manner as in manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on the metal substrate 100 by a plating method.

[0061] Next, the metal substrate 100 on which the first Co film 110, the Re(Ni) film 120, and the second Co film 130 are formed is embedded in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and subjected to heat treatment, thereby simultaneously forming a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500, as shown in Figure 1. When the mixed powder contains Ti powder and Al2O3 powder, for example, it is (10-22) mass% Ti powder + (90-78) mass% Al2O3 powder. In this case, for example, an Al-containing alloy layer 500 with an Al concentration of 10 atomic% to 30 atomic% can be formed. When the mixed powder contains Ti powder, Mg powder, and Al2O3 powder, for example, it is (10-20) mass% Ti powder + (0-2) mass% Mg powder + (90-78) mass% Al2O3 powder. In this case, for example, an Al-containing alloy layer 500 with an Al concentration of 10 atomic% to 55 atomic% can be formed. If the mixed powder contains Mg powder and Al2O3 powder, for example, it is (10-22) wt% Mg powder + (90-78) wt% Al2O3 powder. The heat treatment temperature is for example 1050°C to 1150°C (for example 1100°C), and the time is for example 2 hours to 12 hours. The heat treatment atmosphere is an inert gas atmosphere, preferably for example Ar + 3 vol% H2 atmosphere. The Al concentration of the boundary layer 200 thus formed is typically 25 atomic% or less, preferably 15 atomic% or less. If necessary, powders such as FeAl and NiAl, which serve as Al sources, may be mixed into the mixed powder.

[0062] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0063] (3) Manufacturing method 3 Manufacturing method 3 differs from manufacturing method 2 in that, in addition to sequentially forming a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 on a metal substrate 100 by plating, a Pt film (not shown) is further formed on the second Co film 130 by the same plating method, or Pt powder (not shown) is applied by a slurry method. Otherwise, it is the same as manufacturing method 2. The plating of the Pt film is performed at, for example, a current density of 0.02 A / cm². 2This process is carried out for 1 to 10 minutes. The metal substrate 100, on which the first Co film 110, Re(Ni) film 120, second Co film 130, and Pt film or Pt powder layer have been formed, is then embedded in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and subjected to heat treatment, thereby simultaneously forming a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500, and incorporating Pt into the Al-containing alloy layer 500. The Al concentration of the Al-containing alloy layer 500 to which Pt has been added is, for example, 30 atomic% or more and 40 atomic% or less.

[0064] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0065] (4) Manufacturing method 4 First, in the same manner as in manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on the metal substrate 100 by a plating method.

[0066] Next, the metal substrate 100 on which the first Co film 110, Re(Ni) film 120, and second Co film 130 are formed is embedded in a mixed powder containing Ni powder, NiAl powder, NH4Cl powder, and Al2O3 powder and subjected to heat treatment, thereby simultaneously forming a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500, as shown in Figure 1. The mixed powder is, for example, (1-5) mass% Ni powder + (25-29) mass% NiAl powder + (1-2) mass% NH4Cl powder + (73-64) mass% Al2O3 powder. In this case, for example, an Al-containing alloy layer 500 with an Al concentration of 40 atomic% to 55 atomic% can be formed. The heat treatment temperature is, for example, 950°C to 1100°C, typically 1000°C to 1050°C (e.g., 1100°C), and the time is, for example, 2 hours to 12 hours. The heat treatment atmosphere is an inert gas atmosphere, preferably an Ar + 3 vol% H2 atmosphere.

[0067] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0068] (5) Manufacturing method 5 As shown in Figure 5, in manufacturing method 4, after forming a Ni strike film (not shown) on a metal substrate 100, a Ni-containing Co(Re) alloy film 600 is formed by a plating method using a plating solution obtained by mixing a Co plating solution and a Re(Ni) plating solution. The mixing ratio (vol%) of the Co plating solution and the Re(Ni) plating solution in this plating solution is typically in the range of 10 vol% Co plating solution, 90 vol% Re(Ni) plating solution to 60 vol% Co plating solution, 40 vol% Re(Ni) plating solution, and preferably in the range of 20 vol% Co plating solution, 80 vol% Re(Ni) plating solution to 50 vol% Co plating solution, 50 vol% Re(Ni) plating solution. If necessary, a Ni film (not shown) is further formed on the Co(Re) alloy film 600 by a plating method. The plating conditions for the Ni film are the same as in manufacturing method 1.

[0069] Next, similar to manufacturing method 2, a Co(Re) alloy film 600 containing Ni, or a metal substrate 100 on which a Ni film has been further formed, is embedded in a mixed powder containing Ti powder and / or Mg powder and Al2O3 powder and subjected to heat treatment to simultaneously form a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500.

[0070] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0071] (6) Manufacturing method 6 In manufacturing method 6, similar to manufacturing method 5, a Ni strike film (not shown) is formed on a metal substrate 100, and a Ni-containing Co(Re) alloy film 600 is formed by a plating method using a plating solution obtained by mixing a Co plating solution and a Re(Ni) plating solution. If necessary, a Co film (not shown) is further formed on the Co(Re) alloy film 600 by a plating method. Plating of the Co film is typically performed at a current density of 0.03 A / cm². 2 Do this for 20-60 minutes.

[0072] Next, similar to manufacturing method 1, a Co(Re) alloy film 700 containing Ni, or a metal substrate 100 on which a Co film has been further formed, is embedded in a mixed powder containing Cr powder and Al2O3 powder, and heat treatment is performed in an inert gas atmosphere, for example, an Ar+3vol%H2 atmosphere, at a temperature of, for example, 1050°C to 1150°C (for example, 1100°C) for, for example, 2 to 12 hours, thereby simultaneously forming a boundary layer 200 and a diffusion barrier layer 300.

[0073] Next, in the same manner as in manufacturing method 1, an Al diffusion treatment is performed on the metal substrate 100 on which the boundary layer 200 and diffusion barrier layer 300 have been formed, thereby forming an Al-containing alloy layer 500 on the diffusion barrier layer 300.

[0074] Based on the above, the heat-resistant metal component shown in Figure 1 is manufactured.

[0075] (7) Manufacturing method 7 In manufacturing method 7, similar to manufacturing method 1, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on a metal substrate 100 by plating, and then a Ni film (not shown) is formed on the second Co film 130 by the same plating method.

[0076] Next, the metal substrate 100 on which the first Co film 110, Re(Ni) film 120, second Co film 130, and Ni film have been formed is embedded in a mixed powder containing Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder, and heat-treated (Cr diffusion treatment) is performed to simultaneously form a boundary layer 200, a diffusion barrier layer 300 containing Re and Cr, and a Cr-containing alloy layer 700, as shown in Figure 6. The mixed powder is, for example, (15-25) mass% Ni powder + (10-15) mass% Cr powder + (1-2) mass% NH4Cl powder + (74-58) mass% Al2O3 powder. The heat treatment temperature is, for example, 1050°C to 1150°C (for example, 1100°C), and the time is, for example, 2 hours to 12 hours. The heat treatment atmosphere is an inert gas atmosphere, preferably, for example, an Ar+3vol%H2 atmosphere. The Cr concentration of the Cr-containing alloy layer 700 formed in this way is, for example, between 10 atomic percent and 50 atomic percent. The Cr-containing alloy layer 700 is typically a γ-Co(Cr,Ni) layer and does not contain a high-Cr phase (e.g., an α-Cr phase).

[0077] Next, in the same manner as in manufacturing method 1, the metal substrate 100 on which the boundary layer 200, diffusion barrier layer 300, and Cr-containing alloy layer 700 have been formed is subjected to Al diffusion treatment, thereby converting the Cr-containing alloy layer 700 into an Al-containing alloy layer 500, as shown in Figure 7. At this time, a transition layer 400 containing Cr from the Cr-containing alloy layer 700 is formed between the diffusion barrier layer 300 and the Al-containing alloy layer 500.

[0078] The heat-resistant metal component is manufactured as described above.

[0079] As described above, according to the first embodiment, the heat-resistant metal member has a laminated structure consisting of a boundary layer 200, a diffusion barrier layer 300, and an Al-containing alloy layer 500 on a metal substrate 100. This allows the use of various metal substrates 100, including general-purpose substrates made of Fe-based alloys, Co-based alloys, Ni-based alloys, etc. The diffusion barrier layer 300 provides a continuous diffusion barrier function. Therefore, when the heat-resistant metal member is used in a high-temperature oxidizing or high-temperature corrosive atmosphere, the Al concentration of the Al-containing alloy layer 500 can be maintained at a high level. This allows for the maintenance of a protective Al2O3 film on the outermost surface over a long period of time, resulting in excellent resistance to high-temperature oxidation or corrosion. Furthermore, the formation of voids in the boundary layer 200 can be suppressed, thereby extending the lifespan of the heat-resistant metal member. In addition, the manufacturing process for the heat-resistant metal member is simple, consisting of processes such as plating and packing, thus keeping manufacturing costs low.

[0080] <Second Embodiment> [Heat-resistant metal components] Figure 8 shows a heat-resistant metal member according to the second embodiment. As shown in Figure 8, in this heat-resistant metal member, a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 700 are laminated in this order on the surface of the metal substrate 100. A transition layer 400 may also exist between the diffusion barrier layer 300 and the Cr-containing alloy layer 700, and the laminated structure in that case is shown in Figure 9.

[0081] The metal substrate 100 is the same as in the first embodiment. The boundary layer 200 contains at least Co, and is a layer that also contains one or more elements that constitute the metal substrate 100, one or more elements that constitute the diffusion barrier layer 300, and possibly one or more elements that constitute the Cr-containing alloy layer 700. The boundary layer 200 may or may not contain Al, and the Al concentration and the resulting effects when the boundary layer 200 contains Al are the same as in the first embodiment. The diffusion barrier layer 300 is made of a Co-based alloy containing Re, and contains one or more elements that constitute the metal substrate 100 and one or more elements that constitute the Cr-containing alloy layer 700, and typically has a structure in which an ε-Re(Co) phase is precipitated in a continuous layer of α-Co(Re) phase containing 10 atomic% Re. The diffusion barrier layer 300 helps maintain the Cr concentration of the Cr-containing alloy layer 600 when using heat-resistant metal components, and also facilitates the formation and maintenance of protective Cr2O3, while also exhibiting excellent regeneration capabilities. The transition layer 400 is a layer containing one or more elements that constitute the diffusion barrier layer 300 and one or more elements that constitute the Cr-containing alloy layer 700. The Cr concentration of the Cr-containing alloy layer 700 is not particularly limited, but is typically between 10 atomic% and 50 atomic%, and consists mainly of Co and Ni in addition to Cr. The thicknesses of the boundary layer 200, the diffusion barrier layer 300, and the transition layer 400 are the same as in the first embodiment. The thickness of the Cr-containing alloy layer 700 is the same as that of the Al-containing alloy layer 500.

[0082] [Method for manufacturing heat-resistant metal components] This section describes the manufacturing method for this heat-resistant metal component. Here, we will explain the 8th and 9th examples of the manufacturing method (Manufacturing Methods 8 and 9).

[0083] (1) Manufacturing method 8 First, in the same manner as in manufacturing method 6, a Ni strike film (not shown), a first Co film 110, a Re(Ni) film 120, and a second Co film 130 are sequentially formed on the metal substrate 100 by a plating method. Then, the metal substrate 100, on which the first Co film 110, Re(Ni) film 120, second Co film 130, and Ni film are formed, is embedded in a mixed powder containing Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder and subjected to heat treatment, thereby simultaneously forming a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 700, as shown in Figure 8.

[0084] Based on the above, the heat-resistant metal component shown in Figure 8 is manufactured.

[0085] (2) Manufacturing method 9 First, a first Co film 110, a Re-Ni film 120, and a second Co film 130 are sequentially formed on the metal substrate 100 by plating, in the same manner as in manufacturing method 6.

[0086] Next, a slurry containing a mixed powder (composition for example, 20% by mass Ni powder + 10% by mass Cr powder + 2% by mass NH4Cl powder + 68% by mass Al2O3 powder) is applied to the second Co film 130, dried, and then the metal substrate 100 coated with the slurry is embedded in the mixed powder containing Cr powder and Al2O3 powder and heat-treated to simultaneously form a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 600.

[0087] Based on the above, the heat-resistant metal component shown in Figure 8 is manufactured.

[0088] As described above, according to the second embodiment, the heat-resistant metal member has a laminated structure consisting of a boundary layer 200, a diffusion barrier layer 300, and a Cr-containing alloy layer 700 on a metal substrate 100, so that various metal substrates 100 can be used, including general-purpose substrates such as Fe-based alloys, Co-based alloys, and Ni-based alloys. Furthermore, since the diffusion barrier function can be continuously obtained by the diffusion barrier layer 300, when the heat-resistant metal member is used in a high-temperature oxidizing atmosphere or a high-temperature corrosive atmosphere, the Cr concentration of the Cr-containing alloy layer 700 can be kept high, thereby maintaining a protective Cr2O3 film on the outermost surface for a long period of time, which not only provides excellent resistance to high-temperature oxidation or high-temperature corrosion, but also prevents the formation of voids in the boundary layer 200, thereby extending the lifespan of the heat-resistant metal member, and furthermore, by ensuring that the Cr-containing alloy layer 700 does not contain the α-Cr phase, cracks and peeling of the protective Cr2O3 film can be suppressed. Furthermore, the manufacturing process for heat-resistant metal components is simple, requiring only processes such as plating and packaging, thus keeping manufacturing costs low.

[0089] Examples will be described.

[0090] In the following Examples 1 to 23, the following four types of substrates were used as the metal substrate 100.

[0091] (1) SCH-2 base material (Fe-based alloy base material) (2) SUS310 base material (Fe-based alloy base material) (3) Hastelloy -X base material (Ni-based alloy base material) (4) CMSX-4 base material (Ni-based single crystal superalloy base material)

[0092] The composition (mass%) of each substrate is as follows:

[0093] Elemental composition (mass%) Fe Co Ni Cr Al Mn Mo W Ta Re SCH-2 base material 73 27 SUS310 base material 53 20 25 1.5 Hastelloy -X base material 19 1.5 47 22 0.5 9 CMSX-4 base material 9.6 60 6.6 5.6 0.6 6.4 6.5 3.0

[0094] (Example 1) Example 1 corresponds to the first embodiment.

[0095] A heat-resistant metal component was manufactured using a SUS310 substrate as the metal substrate 100, according to manufacturing method 1.

[0096] First, the surface of the SUS310 substrate was polished smooth and degreased. Then, a Ni strike film, a Co film, a Re(Ni) film, and a Ni film were sequentially formed on the surface by a plating method. The Ni strike film was plated at a current density of 0.5 A / cm². 2 This was done for 1 minute. The Co film plating was performed at a current density of 0.03 A / cm². 2 The process was performed for 10 minutes, and the Re(Ni) and Ni film plating was performed at a current density of 0.04 A / cm². 2 The process was carried out for 10 minutes. The thickness of the Ni strike film was approximately 2 μm, the thickness of the Co film was approximately 10 μm, the thickness of the Re(Ni) film was approximately 4.5 μm, and the thickness of the Ni film was approximately 7.5 μm. Next, the SUS310 substrate on which the plated film was formed was embedded in a mixed powder of Cr powder and Al2O3 powder (10 mass% Cr powder + 90 mass% Al2O3 powder), and heat-treated at 1100°C for 7 hours in an Ar + 3 vol% H2 atmosphere.

[0097] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure and the concentration distribution of each element were observed and measured using a SEM-EDX (Scanning Electron Microscope-Energy Dispersive Spectrometer). Figures 10A and 10B show the cross-sectional SEM image and the measurement results of the concentration distribution of each element measured using EDX (concentration distribution along the analytical line LG1 in the image shown in Figure 10A), respectively. From Figures 10A and 10B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed, which has a structure in which the ε-Re(Co,Ni,Cr,Fe) phase is precipitated in a continuous layer of α-Co(Re) phase with approximately 10 atomic% of Re in solid solution. Figures 11A and 11B show a magnified cross-sectional SEM image of the area around the diffusion barrier layer 300 in Figure 10A and the measurement results of the concentration distribution of Re (concentration distribution along the analytical line LG1 in the image shown in Figure 11A). Figures 11A and 11B show that the Co-based alloy layer containing Re that constitutes the diffusion barrier layer 300 has a structure in which the ε-Re(Co,Ni,Cr,Fe) phase precipitates within a continuous layer of α-Co(Re) phases in which approximately 10 atomic percent of Re is dissolved. The ε-Re(Co,Ni,Cr,Fe) phase is simply denoted as ε-Re(Co) in Figure 11B. The phase relationship between the α-Co(Re) phase and the ε-Re(Co) phase of the diffusion barrier layer 300 can be explained by the Co-Re binary phase diagram shown in Figure 12. Furthermore, Figures 10A and 10B show that a transition layer 400 made of a Ni-Co alloy containing several atomic percent of Fe is observed above the diffusion barrier layer 300. In addition, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300.

[0098] After forming an additional Ni film on the surface of the SUS310 substrate shown in Figure 10A by a plating method, an Al diffusion treatment was performed. The Al diffusion treatment was carried out by immersing the SUS310 substrate shown in Figure 10A in a mixed powder of FeAl powder, NH4Cl powder, and Al2O3 powder (10 mass% FeAl powder + 1 mass% NH4Cl powder + 89 mass% Al2O3 powder) and heating it at 1000°C for 4 hours in an Ar + 3 vol% H2 atmosphere. A portion of the SUS310 substrate / coated surface after the Al diffusion treatment was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 13A and 13B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG3 in the image shown in Figure 13A), respectively. From Figures 13A and 13B, an Al-containing alloy layer 500, mainly composed of Ni and Co in addition to Al, is observed above the transition layer 400. The structures of the boundary layer 200, the diffusion barrier layer 300, and the transition layer 400 are maintained. The concentration of Al contained in the diffusion barrier layer 300 is negligible, and no diffusion of Al into the boundary layer 200 and the SUS310 substrate side is observed.

[0099] (Example 2) Example 2 corresponds to the first embodiment.

[0100] A heat-resistant metal component was fabricated by using a Hastelloy-X substrate as the metal substrate 100 and proceeding with the process in the same manner as in Example 1, up to the Al diffusion treatment.

[0101] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 14A and 14B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG1 in the image shown in Figure 14A), respectively. From Figures 14A and 14B, a boundary layer 200, a diffusion barrier layer 300, a transition layer 400, and an Al-containing alloy layer 500 were observed, similar to Example 1.

[0102] (Example 3) Example 3 corresponds to the first embodiment.

[0103] A heat-resistant metal component was fabricated using manufacturing method 1 with a Hastelloy-X substrate as the metal substrate 100.

[0104] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, a Re(Ni) film, and a Ni film were sequentially formed by a plating method. The thickness of these films and the plating conditions were the same as in Example 1.

[0105] Next, similar to Example 1, the Hastelloy-X substrate on which the plating film was formed was embedded in a mixed powder of Cr powder and Al2O3 powder, and heat-treated at 1100°C for 7 hours in an Ar+3vol%H2 atmosphere.

[0106] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 15A and 15B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 15A), respectively. From Figures 15A and 15B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed, which has a structure in which multiple layers of ε-Re(Co) phase precipitated in a continuous layer of α-Co(Re) phase. Above the diffusion barrier layer 300, a transition layer 400 consisting of a Ni-Co alloy is observed. Similarly, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the Hastelloy-X substrate and the diffusion barrier layer 300.

[0107] Al diffusion treatment was performed on the Hastelloy-X substrate shown in Figure 15A. The Al diffusion treatment was carried out under the same conditions as in Example 1.

[0108] A portion of the Hastelloy-X substrate / coating surface after Al diffusion treatment was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 16A and 16B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG in the image shown in Figure 16A), respectively. From Figures 16A and 16B, it can be seen that the structure of the boundary layer 200 and the diffusion barrier layer 300 shown in Figure 15A is maintained. Despite the high Al concentration of the Al-containing alloy layer 500 (36.4 atomic% to 57.1 atomic%, no diffusion of Al into the boundary layer 200 and the metal substrate 100 was observed.

[0109] Figures 17A and 17B show magnified cross-sectional SEM images of the area around the diffusion barrier layer 300 in Figure 16A, and measurement results of the concentration distribution of Re (concentration distribution along the analytical line LG2 in the image shown in Figure 17A). From Figures 17A and 17B, it can be seen that the Co-based alloy layer containing Re that constitutes the diffusion barrier layer 300 has a multiphase structure in which the ε-Re(Co) phase precipitates within a continuous layer of α-Co(Re) phases in which approximately 10 atomic percent of Re is dissolved.

[0110] (Example 4) Example 4 corresponds to the first embodiment.

[0111] A heat-resistant metal component was fabricated using manufacturing method 2 with a Hastelloy-X substrate as the metal substrate 100.

[0112] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, and a Co film were sequentially formed by plating. The thickness of these films and the plating conditions were the same as in Example 1.

[0113] Next, the Hastelloy-X substrate with the plated film formed in this manner was embedded in a mixed powder of Ti powder and Al2O3 powder (20% by mass Ti powder + 80% by mass Al2O3 powder), and heat-treated at 1100°C for 7 hours in an Ar + 3 vol% H2 atmosphere (Ti treatment).

[0114] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 18A and 18B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 18A), respectively. From Figures 18A and 18B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed, which is composed of a thick continuous layer of α-Co(Re) phase with approximately 10 atomic percent of Re dissolved in it, and a precipitated ε-Re(Co) phase. Above the diffusion barrier layer 300, an Al-containing alloy layer 500 is observed. The Al concentration in the Al-containing alloy layer 500 is 14.0 atomic% to 14.9 atomic% (Max 35.0 atomic%). Between the Hastelloy-X substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed. Al is Hastelloy -Diffusion penetration has occurred on both the X substrate and the boundary layer 200. The transition layer 400 is not observed.

[0115] (Example 5) Example 5 corresponds to the first embodiment.

[0116] A heat-resistant metal component was fabricated using CMSX-4 substrate as the metal substrate 100, according to manufacturing method 2.

[0117] First, the surface of the CMSX-4 substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by a plating method. The thickness of these films and the plating conditions were the same as in Example 1.

[0118] Next, the CMSX-4 substrate on which the plated film had been formed was subjected to the same Ti treatment as in Example 4. However, the Ti treatment was performed for 12 hours.

[0119] A portion of the CMSX-4 substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 19A and 19B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line in the image shown in Figure 19A), respectively. From Figures 19A and 19B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed, which has a structure in which the ε-Re(Co) phase precipitates in a continuous layer of α-Co(Re) phase with approximately 10 atomic percent of Re dissolved in solid solution. Above the diffusion barrier layer 300, a transition layer 400 and an Al-containing alloy layer 500 are observed. The Al concentration in the Al-containing alloy layer 500 is 13.2 atomic% to 14.7 atomic% (Max 36.3 atomic%). Between the CMSX-4 substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed. The Al concentration in the boundary layer 200 is approximately 9 atomic percent, but no Al is detected in the diffusion barrier layer 300. It is thought that the Al present in the boundary layer 200 diffused in from both the CMSX-4 substrate and the Al-containing alloy layer 500, but the Al from the CMSX-4 substrate is dominant, and as a result, the diffusion of Re into the boundary layer 200 appears to be blocked.

[0120] (Example 6) Example 6 corresponds to the first embodiment.

[0121] A heat-resistant metal component was fabricated using manufacturing method 2 with a Hastelloy-X substrate as the metal substrate 100.

[0122] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions were the same as in Example 1.

[0123] Next, the Hastelloy-X substrate on which the plated film was formed was embedded in a mixed powder of Ti powder, Mg powder, and Al2O3 powder (20% by mass Ti powder + 2% by mass Mg powder + 78% by mass Al2O3 powder), and heat-treated at 1100°C for 2 hours in an Ar + 3 vol% H2 atmosphere ((Ti+Mg) treatment).

[0124] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 20A and 20B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 20A), respectively. From Figures 20A and 20B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Between the Hastelloy-X substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed. Above the diffusion barrier layer 300, an Al-containing alloy layer 500 is observed. The Al concentration in the Al-containing alloy layer 500 is high, ranging from 36.3 atomic% to 49.0 atomic%, and diffusion of Al into the boundary layer 200 is observed. A transition layer 400 is not observed.

[0125] (Example 7) Example 7 corresponds to the first embodiment.

[0126] A heat-resistant metal component was fabricated using manufacturing method 2 with a Hastelloy-X substrate as the metal substrate 100.

[0127] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions were the same as in Example 1.

[0128] Next, the Hastelloy-X substrate with the plated film formed in this manner was embedded in a mixed powder of Ti powder, FeAl powder, and Al2O3 powder (20% by mass Ti powder + 2% by mass FeAl powder + 78% by mass Al2O3 powder), and heat-treated at 1100°C for 2 hours in an Ar + 3 vol% H2 atmosphere ((Ti+FeAl) treatment).

[0129] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 21A and 21B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG4 in the image shown in Figure 21A), respectively. From Figures 21A and 21B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Between the Hastelloy-X substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed. Above the diffusion barrier layer 300, a transition layer 400 and an Al-containing alloy layer 500 are observed. The Al concentration in the Al-containing alloy layer 500 is 13.6 atomic% to 18.8 atomic% (Max 37.3 atomic%), indicating that the diffusion of Al towards the boundary layer 200 is suppressed.

[0130] (Example 8) Example 8 corresponds to the first embodiment.

[0131] A heat-resistant metal component was fabricated using manufacturing method 2 with a Hastelloy-X substrate as the metal substrate 100.

[0132] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions were the same as in Example 1.

[0133] Next, the Hastelloy-X substrate with the plated film formed in this manner was embedded in a mixed powder of Ti powder, NiAl powder, and Al2O3 powder (20% by mass Ti powder + 2% by mass NiAl powder + 78% by mass Al2O3 powder), and heat-treated at 1100°C for 2 hours in an Ar + 3 vol% H2 atmosphere ((Ti+NiAl) treatment).

[0134] A part of the Hastelloy-X substrate / coating application surface was cut, and cross-sectional microstructure observation and measurement of the concentration distribution of each element were performed. The measurement results of the cross-sectional SEM photograph and the concentration distribution of each element (concentration distribution along the analysis line LG4 of the photograph shown in Fig. 22A) are shown in Figs. 22A and 22B, respectively. From Figs. 22A and 22B, a diffusion barrier layer 300 composed of a Co-based alloy layer containing Re is observed. Although not shown in the figure, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed between the Hastelloy-X substrate and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed on the upper layer of the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 36.3 atomic% to 49.0 atomic%, and diffusion of Al toward the boundary layer 200 side was recognized.

[0135] (Example 9) Example 9 corresponds to the first embodiment.

[0136] A Hastelloy-X substrate was used as the metal substrate 100, and a heat-resistant metal member was fabricated by Production Method 3.

[0137] First, after treating the surface of the Hastelloy-X substrate in the same manner as in Example 1, a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Pt film were sequentially formed by electroplating. The thickness of the Pt film was about 3 μm. The electroplating of the Pt film was performed at a current density of 0.02 A / cm 2 for 10 minutes. The thicknesses of the films other than the Pt film and the electroplating conditions are the same as in Example 1.

[0138] Next, Ti treatment was performed on the Hastelloy-X substrate on which the electroplated film was thus formed in the same manner as in Example 4.

[0139] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 23A and 23B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG1 in the image shown in Figure 23A), respectively. From Figures 23A and 23B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Between the Hastelloy-X substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration in the Al-containing alloy layer 500 is 31.4 atomic% to 32.7 atomic%, indicating diffusion of Al toward the boundary layer 200.

[0140] (Example 10) Example 10 corresponds to the first embodiment.

[0141] A heat-resistant metal component was fabricated using manufacturing method 3 with a Hastelloy-X substrate as the metal substrate 100.

[0142] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, Co film, Re(Ni) film, Co film, and Pt film were sequentially formed by plating. The thickness of the Pt film and the plating conditions were the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions were the same as in Example 1.

[0143] Next, the Hastelloy-X substrate on which the plated film was formed was subjected to Ti treatment in the same manner as in Example 4.

[0144] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 24A and 24B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line in the image shown in Figure 24A), respectively. From Figures 24A and 24B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Between the Hastelloy-X substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, Mo, etc. is observed. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration in the Al-containing alloy layer 500 is 31.8 atomic% to 35.5 atomic%. Diffusion of Al toward the boundary layer 200 is observed.

[0145] (Example 11) Example 11 corresponds to the first embodiment.

[0146] A heat-resistant metal component was manufactured using manufacturing method 3, with SUS310 as the metal substrate 100.

[0147] First, the surface of the SUS310 substrate was treated in the same manner as in Example 1, and then a Ni strike film, Co film, Re(Ni) film, Co film, and Pt film were sequentially formed by a plating method. The thickness of the Pt film and the plating conditions were the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions were the same as in Example 1.

[0148] Next, the SUS310 substrate on which the plated film was formed was subjected to Ti treatment in the same manner as in Example 4.

[0149] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure and the concentration distribution of each element were observed. Figures 25A and 25B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line in the image shown in Figure 25A), respectively. From Figures 25A and 25B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration in the Al-containing alloy layer 500 is 29.1 atomic% to 33.9 atomic%.

[0150] (Example 12) Example 12 corresponds to the first embodiment.

[0151] A heat-resistant metal component was manufactured using manufacturing method 3, with SUS310 as the metal substrate 100.

[0152] First, the surface of the SUS310 substrate was treated in the same manner as in Example 1, and then a Ni strike film, Co film, Re(Ni) film, Co film, and Pt film were sequentially formed by a plating method. The thickness of the Pt film and the plating conditions were the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions were the same as in Example 1.

[0153] Next, the SUS310 substrate on which the plated film was formed was subjected to Ti treatment in the same manner as in Example 4.

[0154] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 26A and 26B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 26A), respectively. From Figures 26A and 26B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Between the SUS310 substrate and the diffusion barrier layer 300, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed. Above the diffusion barrier layer 300, a transition layer 400 and an Al-containing alloy layer 500 are observed. The Al concentration in the Al-containing alloy layer 500 is 32.9 atomic% to 37.6 atomic%, indicating diffusion of Al towards the boundary layer 200.

[0155] (Example 13) Example 13 corresponds to the first embodiment.

[0156] A heat-resistant metal component was manufactured using manufacturing method 3, with SUS310 as the metal substrate 100.

[0157] First, the surface of the SUS310 substrate was treated in the same manner as in Example 1, and then a Ni strike film, Co film, Re(Ni) film, Co film, and Pt film were sequentially formed by a plating method. The thickness of the Pt film and the plating conditions were the same as in Example 9. The thickness of the films other than the Pt film and the plating conditions were the same as in Example 1.

[0158] Next, the SUS310 substrate on which the plated film was formed was subjected to Ti treatment in the same manner as in Example 4.

[0159] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 27A and 27B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG7 in the image shown in Figure 27A), respectively. From Figures 27A and 27B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300. An Al-containing alloy layer 500 is observed above the diffusion barrier layer 300. The Al concentration in the Al-containing alloy layer 500 is 34.8 atomic% to 41.3 atomic%, indicating Al diffusion toward the boundary layer 200.

[0160] Figure 28 shows the dependence of the Al, Ni, and Co concentrations in Al-containing alloy layer 500, obtained from the results shown in Examples 9-13, on the Pt concentration. From Figure 28, when the Pt concentration was approximately 1.5 atomic percent or higher, the Co concentration decreased, the Ni concentration increased, and the Al concentration increased from 30 atomic percent to 42 atomic percent.

[0161] (Example 14) Example 14 corresponds to the first embodiment.

[0162] A heat-resistant metal component was fabricated using manufacturing method 4 with a SUS310 base material as the metal base material 100.

[0163] First, the surface of the SUS310 substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, and a Co film were sequentially formed by a plating method. The thickness of these films and the plating conditions were the same as in Example 1.

[0164] Next, the SUS310 substrate with the plated film formed in this manner was embedded in a mixed powder of Ni powder, NiAl powder, NH4Cl powder, and Al2O3 powder (3% by mass Ni powder + 10% by mass NiAl powder + 1.5% by mass NH4Cl powder + 16% by mass Al2O3 powder), and heat-treated at 1100°C for 2 hours in an Ar + 3 vol% H2 atmosphere ((Ni+NiAl) treatment).

[0165] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 29A and 29B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line in the image shown in Figure 29A), respectively. From Figures 29A and 29B, it can be seen that a boundary layer 200, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re, a transition layer 400, and an Al-containing alloy layer with an Al concentration of 37.5-44.6 atomic percent are formed. Al diffuses into the boundary layer 200 to a depth of approximately 20 μm.

[0166] (Example 15) Example 15 corresponds to the first embodiment.

[0167] A heat-resistant metal component was fabricated using a SUS310 substrate as the metal substrate 100 and the manufacturing method 7.

[0168] First, the surface of the SUS310 substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by a plating method. The thickness of these films and the plating conditions were the same as in Example 1.

[0169] Next, the SUS310 substrate on which the plating film was formed was embedded in a mixed powder of Ni powder, Cr powder, NH4Cl powder, and Al2O3 powder (20% by mass Ni powder + 10% by mass Cr powder + 1.5% by mass NH4Cl powder + 68% by mass Al2O3 powder), and heat-treated at 1100°C for 8 hours in an Ar + 3 vol% H2 atmosphere ((Cr+Ni) treatment).

[0170] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 30A and 30B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG1 in the image shown in Figure 30A), respectively. From Figures 30A and 30B, it can be seen that a boundary layer 200, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re, and a transition layer 400 are formed. The diffusion barrier layer 300 contains Cr and Fe. The transition layer 400 consists of a γ-Ni(Co,Cr) layer, which is a Cr-containing alloy layer, and the α-Cr phase was not detected.

[0171] Next, the SUS310 substrate shown in Figure 30A was subjected to Al diffusion treatment. The Al diffusion treatment was carried out at 1050°C for 5 hours using the same mixed powder and atmosphere as in Example 1.

[0172] A portion of the SUS310 substrate / coated surface after Al diffusion treatment was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 31A and 31B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG1 in the image shown in Figure 31A), respectively. From Figures 31A and 31B, the structure of the boundary layer 200 and the diffusion barrier layer 300 shown in Figure 30A is maintained. Despite the high Al concentration of 48.1 atomic% to 60.6 atomic% in the Al-containing alloy layer 500, no diffusion of Al into the boundary layer 200 and the metal substrate 100 side was observed. In other words, it can be seen that the diffusion barrier layer 300 formed by the Cr diffusion treatment functions as an Al diffusion barrier. Furthermore, Cr enrichment is observed in the transition layer 400. This is because when Al diffuses into the Ni(Cr) alloy layer, the solubility of Cr in γ'-Ni3Al and β-NiAl is low, so Cr is concentrated on the diffusion barrier layer 300 side.

[0173] (Example 16) Example 16 corresponds to the first embodiment.

[0174] A heat-resistant metal component was fabricated using the manufacturing method 7 with a Hastelloy-X substrate as the metal substrate 100.

[0175] First, the surface of the Hastelloy-X substrate was treated in the same manner as in Example 1, and then a Ni strike film, a Co film, a Re(Ni) film, a Co film, and a Ni film were sequentially formed by plating. The thickness of these films and the plating conditions were the same as in Example 1.

[0176] Next, the Hastelloy-X substrate on which the plated film was formed was subjected to the same (Cr+Ni) treatment as in Example 15.

[0177] A portion of the Hastelloy-X substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 32A and 32B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 32A), respectively. From Figures 32A and 32B, it can be seen that a boundary layer 200 consisting of a Co-containing alloy layer, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re, and a transition layer 400 are formed. The diffusion barrier layer 300 contains Cr and Fe. The transition layer 400 consists of a γ-Ni(Co,Cr) layer, which is a Cr-containing alloy layer, and the α-Cr phase was not detected.

[0178] Next, the Hastelloy-X substrate shown in Figure 32A was subjected to Al diffusion treatment. The Al diffusion treatment was carried out under the same conditions as in Example 15.

[0179] A portion of the Hastelloy-X substrate / coated surface after Al diffusion treatment was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 33A and 33B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG3 in the image shown in Figure 33A), respectively. From Figures 33A and 33B, the structure of the boundary layer 200 and the diffusion barrier layer 300 shown in Figure 32A is maintained. The boundary layer 200 is a Co-containing alloy layer. An Al-containing alloy layer 500 consisting of a β-NiAl layer is observed on the diffusion barrier layer 300. Despite the high Al concentration of the Al-containing alloy layer 500 (45.4 atomic% to 60.17 atomic%, no diffusion of Al into the boundary layer 200 was observed. Cr enrichment is observed in the transition layer 400.

[0180] (Example 17) Example 17 describes a case in which a Co(Re) alloy film containing Ni is formed by a plating method using a plating solution prepared by mixing Co plating solution and Re(Ni) plating solution in various proportions.

[0181] In other words, three different plating solutions with the following mixing ratios were prepared. Co plating solution Re(Ni) plating solution Plating solution (1) 50 vol% 50 vol% Plating solution (2) 25 vol% 75 vol% Plating solution (3) 20 vol% 80 vol%

[0182] The surface of the SUS310 substrate was treated in the same manner as in Example 1 to form a Ni strike film. Then, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (1), and a Ni film was further formed on top of it by a plating method. The plating of the Ni-containing Co(Re) alloy film was performed at a current density of 0.03 A / cm². 2 This was done for 20 minutes. The Ni film plating was performed under the same conditions as in Example 1.

[0183] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 34A and 34B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG1 in the image shown in Figure 34A), respectively.

[0184] The surface of the SUS310 substrate was treated in the same manner as in Example 1 to form a Ni strike film, a Co film was formed by plating, a Ni-containing Co(Re) alloy film was then formed by plating using plating solution (1), and a Co film was further formed on top of that by plating. The plating of the Ni-containing Co(Re) alloy film was performed at a current density of 0.03 A / cm². 2 The process was carried out for 20 minutes. The Ni and Co films were plated under the same conditions as in Example 1. A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 35A and 35B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG3 in the image shown in Figure 35A), respectively.

[0185] After treating the surface of the SUS310 substrate in the same manner as in Example 1, a Ni strike film was formed, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (2), and then a Ni film was formed on top of that by a plating method. The plating of the Ni-containing Co(Re) alloy film was performed at a current density of 0.03 A / cm². 2 The process was carried out for 20 minutes. The Ni film plating was performed under the same conditions as in Example 1. A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 36A and 36B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the image shown in Figure 36A), respectively.

[0186] After treating the surface of the SUS310 substrate in the same manner as in Example 1, a Ni strike film was formed, and a Ni film was formed thereon by a plating method. Subsequently, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (2), and then a Ni film was formed thereon by a plating method. The plating of the Ni-containing Co(Re) alloy film was performed at a current density of 0.03 A / cm². 2 The process was carried out for 20 minutes. The Ni film plating was performed under the same conditions as in Example 1. A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 37A and 37B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG4 in the image shown in Figure 37A), respectively.

[0187] After treating the surface of the SUS310 substrate in the same manner as in Example 1, a Ni strike film was formed, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (3), and then a Ni film was formed on top of that by a plating method. The plating of the Ni-containing Co(Re) alloy film was performed at a current density of 0.03 A / cm². 2 The process was carried out for 20 minutes. The Ni film plating was performed under the same conditions as in Example 1. A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed and the concentration distribution of each element was measured. Figures 38A and 38B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG5 in the image shown in Figure 38A), respectively.

[0188] As described above, the results of forming Ni-containing Co(Re) alloy films using plating solution (1), plating solution (2), and plating solution (3) show the changes in the concentration of each element (Co, Re, Ni) in the Ni-containing Co(Re) alloy film when the volume ratio of Co plating solution in the plating solution is changed. Note that the concentrations of Re and Ni in the Re(Ni) alloy film formed using Re(Ni) plating solution are 40-75 atomic% for Re and 60-25 atomic% for Ni.

[0189] As shown in Figure 39, as the volume ratio of Co plating solution in the plating solution decreases, the Re concentration in the Co(Re) alloy film increases, and the Co concentration decreases from 100% to 0 atomic%. Furthermore, the Ni concentration in the Co(Re) alloy film gradually increases towards the value of the Re(Ni) alloy.

[0190] These results show that by selecting the composition of the plating solution, it is possible to form a Co(Re) alloy film with any Co or Ni concentration.

[0191] (Example 18) Example 18 corresponds to the first embodiment.

[0192] In Example 17, a plating film was formed on a SUS310 substrate using plating solution (1) as shown in Figure 35A. Then, the SUS310 substrate with the plated film was subjected to a Ti treatment to produce a heat-resistant metal component. The Ti treatment was performed in the same manner as in Example 4.

[0193] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 40A and 40B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analysis line LG2 in the image shown in Figure 40A), respectively.

[0194] Figures 40A and 40B show a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re. In the diffusion barrier layer 300, Re is solid-dissolved throughout the Co-based alloy layer. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300. Above the diffusion barrier layer 300, a transition layer 400 and an Al-containing alloy layer 500 are observed. The Al concentration in the Al-containing alloy layer 500 is 6.8 atomic% to 12.8 atomic%. No diffusion of Al toward the boundary layer 200 is observed.

[0195] (Example 19) Example 19 corresponds to the first embodiment.

[0196] In Example 17, a plating film was formed on a SUS310 substrate using plating solution (2) as shown in Figure 36A. Then, the SUS310 substrate with the plated film was subjected to Ti treatment to produce a heat-resistant metal component. The Ti treatment was performed in the same manner as in Example 4.

[0197] A portion of the SUS310 substrate / coated surface was cut, and the cross-sectional microstructure and the concentration distribution of each element were measured. Figures 41A and 41B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG3 in the image shown in Figure 41A), respectively. From Figures 41A and 41B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. In the diffusion barrier layer 300, a Re-enriched layer (20 atomic%) is present in the Co(Re) solid solution. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300. Above the diffusion barrier layer 300, a transition layer 400 and an Al-containing alloy layer 500 are observed. The Al concentration in the Al-containing alloy layer 500 is 4.3 atomic% to 6.6 atomic%, and no diffusion of Al toward the boundary layer 200 is observed.

[0198] (Example 20) Example 20 corresponds to the first embodiment.

[0199] In Example 17, a plating film was formed on a SUS310 substrate using plating solution (3) as shown in Figure 38A. Then, the SUS310 substrate with the plated film was subjected to Ti treatment to produce a heat-resistant metal component. The Ti treatment was performed in the same manner as in Example 4.

[0200] A part of the SUS310 substrate / film application surface was cut, and cross-sectional microstructure observation and measurement of the concentration distribution of each element were performed. The measurement results of the cross-sectional SEM photograph and the concentration distribution of each element (concentration distribution along the analysis line LG4 of the photograph shown in Fig. 42A) are shown in Figs. 42A and 42B, respectively. From Figs. 42A and 42B, a diffusion barrier layer 300 composed of a Co-based alloy layer containing Re is observed. In the diffusion barrier layer 300, a Re-concentrated layer (20 - 25 atomic%) exists in the Co(Re) solid solution. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300. A transition layer 400 and an Al-containing alloy layer 500 are observed above the diffusion barrier layer 300. The Al concentration of the Al-containing alloy layer 500 is 10 atomic% - 40.2 atomic%, and Al diffusion toward the boundary layer 200 side is recognized.

[0201] (Example 21) Example 21 corresponds to the first embodiment.

[0202] After treating the surface of the SUS310 substrate in the same manner as in Example 1, a Ni strike film was formed, a Co(Re) alloy film containing Ni was formed by electroplating using electroplating solution (2), and then a Co film was formed thereon by electroplating. Next, the SUS310 substrate on which such an electroplated film was formed was buried in a mixed powder of Cr powder and Al2O3 powder (10 mass% Cr powder + 90 mass% Al2O3 powder), and heated at 1100 °C for 2 hours in an Ar + 3 vol% H2 atmosphere.

[0203] A part of the SUS310 substrate / film application surface was cut, and cross-sectional microstructure observation and measurement of the concentration distribution of each element were performed. The measurement results of the cross-sectional SEM photograph and the concentration distribution of each element (concentration distribution along the analysis line LG3 of the photograph shown in Fig. 43A) are shown in Figs. 43A and 43B, respectively. From Figs. 43A and 43B, a diffusion barrier layer 300 composed of a Co-based alloy layer containing Re is observed. Also, a transition layer 400 composed of a Ni-Co alloy containing Fe is observed above the diffusion barrier layer 300. A boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300.

[0204] Although not shown in the diagram, an Al-containing alloy layer 500 was formed as the uppermost layer by performing an Al diffusion treatment in the same manner as in Example 1.

[0205] (Example 22) Example 22 corresponds to the first embodiment.

[0206] After treating the surface of the SCH-2 substrate in the same manner as in Example 1, a Ni strike film was formed, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (2), and then a Co film was formed on top of that by a plating method. Next, the SCH-2 substrate with the plated film thus formed was subjected to the same heat treatment as in Example 21.

[0207] A portion of the SCH-2 substrate / coated surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 44A and 44B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG2 in the image shown in Figure 44A), respectively. From Figures 44A and 44B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Above the diffusion barrier layer 300, a transition layer 400 consisting of a Ni-Co alloy containing Fe is observed. Furthermore, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300.

[0208] Although not shown in the diagram, an Al-containing alloy layer 500 was formed as the uppermost layer by performing an Al diffusion treatment in the same manner as in Example 1.

[0209] (Example 23) Example 23 corresponds to the first embodiment.

[0210] After treating the surface of the Hastelloy-X substrate in the same manner as in Example 1, a Ni strike film was formed, a Ni-containing Co(Re) alloy film was formed by a plating method using plating solution (2), and then a Co film was formed on top of that by a plating method. Next, the Hastelloy-X substrate with the plated film thus formed was subjected to the same heat treatment as in Example 21.

[0211] A portion of the Hastelloy-X substrate / coating surface was cut, and the cross-sectional structure was observed, along with the measurement of the concentration distribution of each element. Figures 45A and 45B show the cross-sectional SEM images and the measurement results of the concentration distribution of each element (concentration distribution along the analytical line LG1 in the image shown in Figure 45A), respectively. From Figures 45A and 45B, a diffusion barrier layer 300 consisting of a Co-based alloy layer containing Re is observed. Above the diffusion barrier layer 300, a transition layer 400 consisting of a Ni-Co alloy containing Fe is observed. Furthermore, a boundary layer 200 containing Co, Ni, Fe, Cr, etc. is observed between the SUS310 substrate and the diffusion barrier layer 300.

[0212] Although embodiments and examples of this invention have been described in detail above, this invention is not limited to the embodiments and examples described above, and various modifications based on the technical idea of ​​this invention are possible.

[0213] In the invention of a method for manufacturing a heat-resistant metal member described herein, multiple layers of various metal films are sequentially formed on a metal substrate by a plating method. In its broadest sense, the metal film formed on a metal substrate by a plating method can be described as a metal film containing Co, Re, and Ni as a whole. This metal film may be a single layer or multiple layers. For example, in the invention of a method for manufacturing a heat-resistant metal member in which at least a first Co film, an Re(Ni) film, and a second Co film or Ni film are sequentially formed on a metal substrate, a single or multiple layers of metal film containing Co, Re, and Ni as a whole may be formed instead of the first Co film, the Re(Ni) film, and the second Co film or Ni film. The first Co film, the Re(Ni) film, and the second Co film or Ni film are examples of such metal films. [Explanation of symbols]

[0214] 100...Metal substrate, 200...Boundary layer, 300...Diffusion barrier layer, 400...Transition layer, 500...Al-containing alloy layer, 700...Cr-containing alloy layer

Claims

1. Metal substrate and A diffusion barrier layer on the above metal substrate, comprising at least a Co-based alloy containing Re as its main component, A boundary layer containing at least Co between the above-mentioned metal substrate and the above-mentioned diffusion barrier layer, The above diffusion barrier layer includes an Al-containing alloy layer or a Cr-containing alloy layer, A heat-resistant metal component having the following properties.

2. The heat-resistant metal member according to claim 1, wherein the diffusion barrier layer consists of an α-Co(Re) continuous layer containing 10 atomic percent of Re, and the α-Co(Re) continuous layer contains precipitates of the ε-Re(Co) phase.

3. The heat-resistant metal member according to claim 1, having the above-mentioned Al-containing alloy layer on the above-mentioned diffusion barrier layer, wherein the Al-containing alloy layer contains Pt.

4. The heat-resistant metal member according to claim 1, having the above-mentioned Al-containing alloy layer on the above-mentioned diffusion barrier layer, wherein the boundary layer contains Al.

5. The heat-resistant metal member according to claim 4, wherein the Al concentration of the boundary layer is 1 atomic% or more and 25 atomic% or less.

6. The heat-resistant metal member according to claim 1, having the above-mentioned Al-containing alloy layer on the above-mentioned diffusion barrier layer, wherein the above-mentioned Al-containing alloy layer mainly consists of Co and Ni in addition to Al.

7. The heat-resistant metal member according to claim 1, having the above-mentioned Cr-containing alloy layer on the above-mentioned diffusion barrier layer, wherein the above-mentioned Cr-containing alloy layer mainly consists of Co and Ni in addition to Cr.

8. The heat-resistant metal member according to claim 1, further comprising a transition layer between the above-mentioned diffusion barrier layer and the above-mentioned Al-containing alloy layer or the above-mentioned Cr-containing alloy layer.

9. The heat-resistant metal member according to claim 8, wherein the transition layer has a Re concentration of less than 1 atomic percent and an Al concentration of 10 atomic percent or less.

10. The heat-resistant metal member according to claim 1, wherein the metal substrate is an Fe-based alloy, a Co-based alloy, a Ni-based alloy, or a Ni-based single-crystal superalloy.

11. A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, The metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed is made of Cr powder and Al 2 O 3 A step of forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer, on which at least Re-containing Co-based alloy is the main component, by immersing in a mixed powder containing the powder and performing heat treatment, A step of forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer and the diffusion barrier layer are formed, A method for manufacturing a heat-resistant metal member having the following characteristics.

12. A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, The metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed is coated with Ti powder and / or Mg powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer mainly composed of a Co-based alloy containing Re, and an Al-containing alloy layer on the diffusion barrier layer by immersing in a mixed powder containing powder and performing heat treatment, A method for manufacturing a heat-resistant metal member having the following characteristics.

13. A method for manufacturing a heat-resistant metal member according to claim 12, wherein, after forming the second Co film described above, and before performing the heat treatment described above, a Pt film is formed on the second Co film by a plating method, or Pt powder is applied by a slurry method.

14. A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, The metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed is made of Ni powder, NiAl powder, and NH 4 Cl powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer mainly composed of a Co-based alloy containing Re, and an Al-containing alloy layer on the diffusion barrier layer by immersing in a mixed powder containing powder and performing heat treatment, A method for manufacturing a heat-resistant metal member having the following characteristics.

15. A step of forming a Co(Re) alloy film containing at least Ni on a metal substrate by a plating method using a plating solution obtained by mixing a Co plating solution and a Re(Ni) plating solution, The metal substrate on which the Co(Re) alloy film is formed is buried in a mixed powder containing Ti powder and / or Mg powder and Al 2 O 3 powder, and heat treatment is performed to simultaneously form at least a boundary layer containing Co, a diffusion barrier layer mainly composed of a Co-based alloy containing Re on the boundary layer, and an Al-containing alloy layer on the diffusion barrier layer A method for manufacturing a heat-resistant metal member having the following characteristics.

16. A method for manufacturing a heat-resistant metal member according to claim 15, wherein after forming the above-mentioned Co(Re) alloy film and before performing the above-mentioned heat treatment, a Ni film is formed on the above-mentioned Co(Re) alloy film by a plating method.

17. A step of forming a Co(Re) alloy film containing at least Ni on a metal substrate by a plating method using a plating solution obtained by mixing a Co plating solution and a Re(Ni) plating solution, The above metal substrate on which the above Co(Re) alloy film is formed is made of Cr powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co and a diffusion barrier layer on the boundary layer, on which at least Re-containing Co-based alloy is the main component, by embedding in a mixed powder containing the powder and performing heat treatment, A step of forming an Al-containing alloy layer on the diffusion barrier layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer and the diffusion barrier layer are formed, A method for manufacturing a heat-resistant metal member having the following characteristics.

18. A method for manufacturing a heat-resistant metal member according to claim 17, wherein, after forming the above-mentioned Co(Re) alloy film and before performing the above-mentioned heat treatment, a Co film is formed on the above-mentioned Co(Re) alloy film by a plating method.

19. A step of sequentially forming at least a first Co film, a Re(Ni) film, a second Co film, and a Ni film on a metal substrate by a plating method, The metal substrate on which the first Co film, the Re(Ni) film, the second Co film, and the Ni film are formed is made up of Ni powder, Cr powder, and NH 4 Cl powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer mainly composed of a Co-based alloy containing Re, and a Cr-containing alloy layer on the diffusion barrier layer by immersing in a mixed powder containing powder and performing heat treatment, A step of converting the Cr-containing alloy layer into an Al-containing alloy layer by performing an Al diffusion treatment on the metal substrate on which the boundary layer, the diffusion barrier layer, and the Cr-containing alloy layer are formed, A method for manufacturing a heat-resistant metal member having the following characteristics.

20. A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, The metal substrate on which the first Co film, the Re(Ni) film, and the second Co film or Ni film are formed is made of Ni powder, Cr powder, and NH 4 Cl powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer mainly composed of a Co-based alloy containing Re, and a Cr-containing alloy layer on the diffusion barrier layer by immersing in a mixed powder containing powder and performing heat treatment, A method for manufacturing a heat-resistant metal member having the following characteristics.

21. A step of sequentially forming at least a first Co film, a Re(Ni) film, and a second Co film or Ni film on a metal substrate by a plating method, On the second Co film described above, at least Ni powder, Cr powder, and NH 4 Cl powder and Al 2 O 3 After applying a slurry containing a mixed powder including Cr powder, the metal substrate to which the slurry has been applied is then treated with Cr powder and Al 2 O 3 A step of simultaneously forming a boundary layer containing at least Co, a diffusion barrier layer on the boundary layer mainly composed of a Co-based alloy containing Re, and a Cr-containing alloy layer on the diffusion barrier layer by immersing in a mixed powder containing powder and performing heat treatment, A method for manufacturing a heat-resistant metal member having the following characteristics.

22. Metal substrate and A diffusion barrier layer on the above metal substrate, comprising at least a Co-based alloy containing Re as its main component, A boundary layer containing at least Co between the above-mentioned metal substrate and the above-mentioned diffusion barrier layer, The above diffusion barrier layer includes an Al-containing alloy layer or a Cr-containing alloy layer, Heat-resistant metal member having A high-temperature device having the following features.

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